CN1781953A - Method for continuously producing polyethylene - Google Patents
Method for continuously producing polyethylene Download PDFInfo
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- CN1781953A CN1781953A CN 200410091277 CN200410091277A CN1781953A CN 1781953 A CN1781953 A CN 1781953A CN 200410091277 CN200410091277 CN 200410091277 CN 200410091277 A CN200410091277 A CN 200410091277A CN 1781953 A CN1781953 A CN 1781953A
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Abstract
The present invention relates to continuous polyethylene producing process to produce multiple section polymerized resin composition. The production process includes the stage A of preparing polyethylene of limit viscosity 0.1-4.0, the stage B of preparing polyethylene of limit viscosity 1.0-7.0, the stage C of preparing polyethylene of limit viscosity 1.0-7.0, and the stage D of preparing polyethylene of limit viscosity 2.0-11.5. The resin composition has limit viscosity range of 1.1-8.0, density range of 0.935-0.965 g/cu cm, excellent environment stress tolerance and excellent rigidity, and may be used in making product with excellent outer appearance and no fish eye and gel faults.
Description
Technical field
The invention belongs to the technical field of polyethylene production, relate in particular to a kind of multi-stage polymeric manufacturing process of polyethylene resin composition, described resin is because of having wide or bimodal molecular weight distribution, help making and have good environmental stress crack resistance (hereinafter to be referred as ESCR) and excellent inflexible slush molding chemistry bucket (drum) and extrusion molding tubing, not only the inwall of shaped material and outward appearance are good, and there is not a defective of flake or gel, more particularly, the present invention relates to comprise the molding performance of having improved resin, and make the manufacture method of production cost reduction because of the increase of catalyst activity.
Background technology
In recent years, along with continuing to bring out of new technology and product innovation, the consumption market is increasing to the demand of high-performance polyethylene, but relatively, and for example the requirement of intensity, rigidity and ESCR is also more and more higher to poly processing characteristics.Improve molecular weight and can improve poly these performances, surpass 250,000 HMW (high molecular weight)-high density polyethylene as the preparation relative molecular weight.But, when having increased poly molecular weight, extrude, the processibility of molding, thermoforming and rotational molding performance also descends thereupon, polyethylene broad or bimodal molecular weight distribution can solve these shortcomings well, because the polymkeric substance long-chain provides physical strength, there has been the polymkeric substance short chain that lubrication is provided again exactly.In addition, the distribution of control copolymerization monomer is also very important, and in other words, the bonding properties of copolymerization monomer on relative high-molecular weight chain will be got well; Then by chance opposite on low-molecular-weight relatively chain.Generally speaking, molecular weight distribution is an important factor that influences ESCR, because molecular weight distribution has directly reflected macromole and micromolecular content in the polymkeric substance.Macromolecular content is many more, and chip chamber link molecule number will be many more, and the ESCR performance is good more.And density and degree of crystallinity are more complicated to the influence of ESCR, and density is big more on the one hand, and degree of crystallinity is high more, and the link molecule number of chip chamber tails off, and cause ESCR to descend; Though poly density is lower, perhaps higher limiting viscosity makes polymkeric substance have ESCR preferably,, when density polymer reduced, the physical strength of resin combination and rigidity also can descend.When polyethylene had higher limiting viscosity or higher molecular weight, it is very poor that resin flow but becomes, thereby caused the problem of moulding.Therefore, under the situation of control density of pe, improve polyvinyl resin ESCR and pin down mutually between the two, must obtain a balance with the raising rigidity.
As everyone knows, adopting aq slurry process is one of the method for the polyethylene with wide molecular weight distribution of production blowing, there have been many researchs to make the method for the polymkeric substance of wide molecular weight distribution with Ziegler (Ziegler) catalyzer in this respect, for example, document [Macromolecular.Symp., 163,135-143 (2001)] disclosed through two tandem reactors and made lower molecular weights and High molecular weight polyethylene method for compositions, and the technology of many multi-stage polymerics is proposed.Offer [Plastics in a separate paper; Rubber and Composites Processing and Applications, 25 (8), 368-372 (1996)] and document [Shanghai chemical industry; the 8th phase, 21-25 (2002)] then reported poly technology of various manufacturing bimodal distributions and technology.Generally speaking, contrast is by the resulting polyethylene of one-step polymerization method, and the polyethylene resin composition that obtains by two sections polymerization processs has more excellent ESCR and inflexible over-all properties.For example, Japanese patent laid-open 2-155906, spy open and have disclosed a kind of copolymerization may command polyethylene inflexible method with alpha-olefin among clear 64-1709 and the clear 64-79204 of Te Kai, simultaneously ESCR and inflexible over-all properties can show and improving by sneaking into alpha-olefin, and the alpha-olefin content in higher molecular weight section polymkeric substance is greater than the alpha-olefin content in lower molecular weight section polymkeric substance like this.Yet the blow molded product that obtains by this two sections polymerization processs still has the bond strength deficiency of the part of cutting the base mouth, and the less shortcoming of ratio of expansion.
In order to overcome above-mentioned shortcoming, the Japanese Patent spy opens clear 62-25105～25109, spy and opens clear 61-130310, special public clear 59-10724, special public clear 62-61057, special fair 3-29805, special fair 4-14686, spy and open clear 58-138719, spy and open clear 59-227913, spy and open the method that clear 64-79204 etc. discloses three stage polymerization, has mentioned the polyethylene co-polymer of three kinds of different molecular weights of continuous manufacturing.But as opening the Japanese Patent spy clear 59-227913 and the clear 61-207404 of Te Kai point out, although the poly ratio of expansion that obtains can obtain improvement, the over-all properties of rigidity and ESCR is not good.And, in the three stage polymerization method that proposes by existing technology, except making lower molecular weight and high molecular weight fraction present, also made a spot of ultra-high molecular weight component usually by two sections common polymerization processs, tend to form the defective of flake or gel like this, be unfavorable for processing.Chinese patent CN1405224A has also proposed the manufacture method of the polyethylene resin composition of another kind of three stage polymerization, the method of discovery by making three kinds to have the polymkeric substance generation of non-ultra-high molecular weight component, and further all differ and be not very big by the amount of polymers that limits limiting viscosity (being equivalent to the molecular weight size) between component in this polymkeric substance (B) and the component (C) and step (b) and step (c), make the compatibility of polymkeric substance each component approaching, the result combinations resin very evenly and not can form gel, defective or flake.But the manufacture method of such composition is close for amount of polymers and the molecular weight of controlling second section and the 3rd section, should be with step (a), step (b) is step (c) or step (b) then, step (a) the then such order of step (c) is made continuously, and because the density of hydrogen of back segment is lower than the density of hydrogen of leading portion, therefore hydrogen blows that to drive (purge) be necessary, that is to say, which kind of order no matter such manufacture method adopt, for example from step (a), step (b) is step (c) or step (b) then, step (a) is step (c) then, in order to realize that aforementioned control component of mentioning (B) and the limiting viscosity between the component (C) differ the purpose that is not very big, so each step all must be through heating up after degassing vessel (flush tank) release of pressure and the cooling again.In addition, in order in the component of step (c), to contain the alpha-olefin of more amount, alpha-olefin addition in step (c) is higher than in step (a) and step (b), has brought inconvenience and has not been inconsistent cost to suitability for industrialized production like this, is unfavorable for the industrial production of serialization.
Summary of the invention
Technical problem to be solved by this invention is the method for continuous production that solves an above-mentioned difficult problem, a kind of polyvinyl resin is provided.
Technical scheme provided by the present invention is: in four reactors of configured in series starting monomer is carried out polyreaction and mixing, at least one reactor wherein, except that necessary starting monomer, also use a kind of in the solid catalyst of the solid catalyst metallocene compound contain (a) titanium Beauteous and halogenide component at least and aikyiaiurnirsoxan beta, and (b) molectron of organo-aluminium compound, well carries out the engineering that the multistage successive polymerization mixes simultaneously with the reactor that other is supplied with starting monomer, make limiting viscosity [η] scope from 1.1 to 8.0 with resin combination at last, density range is from 0.935g/cm
3To 0.965g/cm
3Polyethylene, the engineering a.b that is carried out in each reactor wherein, the control condition of c.d is:
Engineering a: under 70～100 ℃ of temperature, (dl/g) Alathon of scope from 0.1 to 4.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt% of manufacturing limit viscosity [η];
Engineering b: under 60～90 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 1.0 to 7.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering c: under 60～90 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 1.0 to 7.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering d: under 40～70 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 2.0 to 11.5 or the alpha-olefin content ethylene copolymer from 0 to 4.5wt%;
Wherein:
(1) content of the Alathon of engineering a, engineering b and engineering c manufacturing or multipolymer respectively accounts for the polymkeric substance total amount from 20wt% to 50wt%;
(2) content of the Alathon of engineering d manufacturing or multipolymer accounts for the polymkeric substance total amount from 0.5wt% to 10wt%;
(3) according to (engineering b amount of polymers+engineering c amount of polymers): engineering a amount of polymers=6/7～5/1 adjusts;
(4) engineering d uses hydrogen or alcohols to work as molecular weight regulator.
Described engineering a, engineering b, engineering c and engineering d can make tactic arbitrarily change under described each control condition, but the configuration of placed in-line each reactor do not change, to carry out polyreaction.
Described polyethylene is Alathon or ethylene copolymer.
Described ethylene copolymer is an alpha-olefin content from 0 to 10wt% ethylene copolymer.
Advantage of the present invention is: molecular weight and molecular weight distribution are done arbitrarily and are regulated, also has good melt fluidity, not only have LMWC and high molecular weight fraction present simultaneously, and contain a spot of extra high molecular amount component, specifically, the molecular weight of extra high molecular amount component is between high molecular and ultra-high molecular weight.Resin helps making hollow forming chemistry bucket and extrusion molding tubing with good ESCR, excellent rigidity and intensity because of having wide or bimodal molecular weight distribution, do not have the defective of flake or gel, and molding performance is good.
Description of drawings
Fig. 1 is the schema of the poly method for continuous production of the present invention.
Embodiment
Below describe the specific embodiment of the present invention in detail with regard to schema shown in the accompanying drawing.
As shown in Figure 1, polyethylene method for continuous production of the present invention belongs to a kind of four sections polymeric methods, comprises four placed in-line being used for respectively at the Alathon of each tool otherwise limit viscosity [η] of manufacturing or the reactor of the ethylene copolymer of alpha-olefin content in deciding scope under the different specific temperature conditions.
Reactor 1～4 preferably adopts the inner autoclave that agitator is housed.Raw material comprises ethene and 'alpha '-olefin monomers and solvent, also has catalyzer and organo-aluminium compound.These raw materials drop into or import in each reactor in existing mode, and carry out polyreaction under different control condition, with the different polyethylene of manufacturing limit viscosity [η].Polyethylene can be an Alathon, also can be ethylene copolymer.In each reactor, carry out the engineering of polyreaction, be docile and obedient preface with engineering a, engineering b engineering c and engineering d representative, because engineering a is that series connection one row carry out continuously from the upstream to the downstream to engineering d, so can enter the mixed with polymers reaction of gained among engineering b and the engineering b by the polymkeric substance of engineering a gained after, the polymkeric substance that enters gained among engineering c and the engineering c mixes again, and the polymkeric substance that then enters gained among engineering d and the engineering c mixes, and can get final desired polyvinyl resin at last.
Catalyzer and organo-aluminium compound only drop into usually first reactor be among the engineering a as shown in Figure 1, but do not limit and only do not drop into first reactor, any in second to the 4th reactor or a plurality ofly also can drop into where necessary.
Catalyzer mainly is to use the solid Z-type catalyst of titanium, magnesium and halogenide component or the solid catalyst of metallocene compound and aikyiaiurnirsoxan beta, all is can buy on the market or can prepare voluntarily.
More particularly, the present invention is a kind of four-part form method for continuous production of polyvinyl resin, it is in manufacturing processed, at least in first reactor, except as the ethene of raw material and/or the solid catalyst of 'alpha '-olefin monomers and compound and aikyiaiurnirsoxan beta, and the molectron of organo-aluminium compound carries out the ethene homogeneous polymerization of multistage or ethylene copolymerization also mixes simultaneously, to make final polyethylene resin composition, this resin combination has limiting viscosity [η] scope from 1.1 to 6.0, density range from 0.935 to 0.965g/cm
3, method comprises followingly can random order carry out following engineering step:
The present invention uses and contains the solid Z-type catalyst of (a) titanium, magnesium and halogenide component or the solid catalyst of metallocene compound and aikyiaiurnirsoxan beta at least, and (b) combined system of organo-aluminium compound carries out the ethene homogeneous polymerization of multistage or the method for continuous production of ethylene copolymerization, the limiting viscosity of described resin combination [η] scope from 1.1 to 8.0, density range from 0.935 to 0.965g/cm
3, it comprises and can random order carry out the following step:
Engineering a: under 70～100 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 0.1 to 4.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering b: under 60～90 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 1.0 to 7.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering c: under 60～90 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 1.0 to 7.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering d: under 40～70 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 2.0 to 11.5 or the alpha-olefin content ethylene copolymer from 0 to 4.5wt%.
Use the combination of above-mentioned solid catalyst and organo-aluminium compound to carry out the multistage successive polymerization, like this at engineering a, the Alathon of engineering b and engineering c manufacturing or the content of multipolymer respectively account for the polymkeric substance total amount from 20 to 50wt%, be preferably from 25 to 45wt%, the Alathon that engineering d makes or the content of multipolymer account for the polymkeric substance total amount from 0.5 to 10wt%, be preferably from 2 to 6wt%, and (engineering b amount of polymers+engineering c amount of polymers): engineering a amount of polymers=6/7～5/1, be preferably from 1/1 to 3/1, just can obtain having limiting viscosity [η] scope from 1.1 to 8.0, density range from 0.935 to 0.965g/cm
3The resin combination of bimodal distribution.The amount of polymers of each engineering not only can be done according to the characteristic of product and client's demand and adjust and design (polymer design) arbitrarily, very flexible, and because the residence time of polyreaction prolongs, make activity of such catalysts significantly improve, production efficiency increases, cost descends, and purpose of the present invention also can realize.
Except ethene, with the copolymerization monomer of alpha-olefin as the present invention's use, should use the alpha-olefin that contains 3 to 20 carbon numbers, a kind of in propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecylene or the 1-eicosylene for example, wherein 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene are first-selected.In slurry polymerization, the solvent of use can be aliphatic propane, butane, pentane, hexane, heptane, octane, dodecane, pentamethylene, hexanaphthene or methylcyclopentane; Aromatic benzene, toluene or dimethylbenzene, wherein hexane and heptane are first-selected.
Make the present invention and comprised, and these engineering steps can be carried out with order arbitrarily from the resin combination of the polyvinyls of the multistage successive polymerization of engineering a, engineering b, engineering c and engineering d.Engineering a carries out in from 70 to 100 ℃ of polymerization temperature scopes, preferably from 75 to 95 ℃, be more preferably under from 75 to 85 ℃ the condition and carry out, select such scope to be because if polymerization temperature above 100 ℃, partly polymkeric substance will fusion, and the formation agglomeration, thereby remain in operation the very difficulty that becomes; If polymerization temperature is less than 70 ℃, catalyst activity is too low, and polyreaction is difficult for carrying out, and production cost increases.In this engineering a, manufacturing has the ethylene homo compound of limit viscosity [η] scope from 0.1 to 4.0 or has the ethylene copolymer of alpha-olefin content from 0 to 10wt%, better is the ethylene homo compound of limit viscosity [η] scope from 0.2 to 2.5 or alpha-olefin content from 0.1 to 2.5wt% ethylene copolymer.When alpha-olefin content greater than 10wt%, the rigidity of resin combination is step-down, and the solvable composition of co-polymer in solvent increases.When limit viscosity [η] less than 0.1 the time, the bond strength of cutting base oral area part of blow molded product is often not enough, if but limit viscosity [η] greater than 4.0 o'clock, the ESCR of resin combination again can variation.
Then engineering b carries out in from 60 to 90 ℃ of polymerization temperature scopes, preferably from 65 to 85 ℃, be more preferably under from 70 to 80 ℃ the condition and carry out, select such scope to be because if polymerization temperature above 90 ℃, not only partly polymkeric substance will fusion and is formed agglomeration, thereby remain in operation the very difficulty that becomes, while productivity can reduce and limiting viscosity also becomes is difficult to control; If polymerization temperature is less than 60 ℃, catalyst activity is too low, and polyreaction is difficult for carrying out, and production cost increases.And in this engineering b, manufacturing has the ethylene homo compound of limit viscosity [η] scope from 1.0 to 7.0 or has the ethylene copolymer of alpha-olefin content from 0 to 10wt%, better is the ethylene homo compound of limit viscosity [η] scope from 1.5 to 5.6 or alpha-olefin content from 0.1 to 1.5wt% ethylene copolymer.When alpha-olefin content greater than 10wt%, the rigidity of resin combination is variation, and co-polymer solvable composition in solvent increases, subsequent disposal is difficulty relatively.When limit viscosity [η] less than 1.0 the time, the impact strength of resin combination is often not enough, if but limit viscosity [η] surpasses at 7.0 o'clock, the flowability of resin combination is with regard to variation, and flake or gel just are easy to occur in the product of hollow forming or extrusion molding.
Then engineering c carries out in from 60 to 90 ℃ of polymerization temperature scopes, preferably from 65 to 85 ℃, be more preferably under from 70 to 80 ℃ the condition and carry out, select such scope to be because if polymerization temperature above 90 ℃, not only partly polymkeric substance will fusion and is formed agglomeration, thereby remain in operation the very difficulty that becomes, while productivity can reduce and limiting viscosity also becomes is difficult to control; If polymerization temperature is less than 60 ℃, catalytic activity is too low, and polyreaction is difficult for carrying out, and production cost increases.And in this engineering c, manufacturing has the ethylene homo compound of limit viscosity [η] scope from 1.0 to 7.0 or has the ethylene copolymer of alpha-olefin content from 0 to 10wt%, better is the ethylene homo compound of limit viscosity [η] scope from 1.5 to 5.6 or alpha-olefin content from 0.1 to 1.5wt% ethylene copolymer.When alpha-olefin content greater than 10wt%, the rigidity of resin combination is variation, and the solvable composition of co-polymer in solvent increases.When limit viscosity [η] less than 1.0 the time, the impact strength of resin combination is often not enough, if but limit viscosity [η] was above 7.0 o'clock, the flowability of resin combination is deficiency, and the restriction reason that here limits in the resin component of the reason of limit viscosity [η] and alpha-olefin content and aforementioned engineering b is the same.
Arrive engineering d at last, in from 40 to 70 ℃ of polymerization temperature scopes, carry out, preferably from 45 to 65 ℃, be more preferably under from 45 to 55 ℃ the condition and carry out, selecting such scope is that catalytic activity is too low, is not inconsistent cost because if polymerization temperature is lower than 40 ℃; If polymerization temperature surpasses 70 ℃, limiting viscosity [η] will become and be difficult to control.And in this engineering d, manufacturing has the ethylene homo compound of limit viscosity [η] scope from 2.0 to 11.5 or has the ethylene copolymer of alpha-olefin content from 0 to 4.5wt%, better is the ethylene homo compound of limit viscosity [η] scope from 4.5 to 9.5 or alpha-olefin content from 0 to 0.5wt% ethylene copolymer.When alpha-olefin content greater than 4.5wt%, polymerization temperature must reduce, productivity will descend.When limit viscosity [η] less than 2.0 the time, the impact strength of resin combination is often not enough, if but limit viscosity [η] surpasses at 11.5 o'clock, the flowability of resin combination is with variation, and the defective of flake or gel just is easy to occur in the product of hollow forming or extrusion molding.
The Alathon of engineering a of the present invention, engineering b and engineering c manufacturing or the content of multipolymer respectively account for the polymkeric substance total amount from 20 to 50wt%, be preferably in 25 to 45wt% scope and do adjusting, the Alathon that engineering d makes or the content of multipolymer account for the polymkeric substance total amount from 0.5 to 10wt%, be preferably in 2.0 to 6.0wt% scope and do adjusting, and (engineering b amount of polymers+engineering c amount of polymers): engineering a amount of polymers=6/7～5/1 is preferably from 1/1 to 3/1.When the amount of polymers of engineering a during less than 20wt%, the flowability of resin combination is with variation, and the mouldability in blowing or extrusion moulding is poor.On the other hand, if when surpassing 50wt%, flake or gel tend to increase.When the amount of polymers of engineering b or engineering c was too low, the ESCR of resin combination tended to variation, and when too high, the rigidity of resin combination is with step-down.When the amount of polymers of engineering d during less than 1wt%, the impact strength of resin combination is often not enough, if when surpassing 10wt%, flake or gel also can increase.
In the present invention, the limiting viscosity of each engineering has shown that engineering a is used for making LMWC, engineering b and engineering c are used for making high molecular weight fraction present, engineering d is used for making extra high molecular amount component, and the molecular weight of extra high molecular amount component is between high molecular and ultra-high molecular weight.Though engineering d makes extra high molecular amount component, but when making a small amount of extra high molecular weight polymers, the invention provides a kind of method of avoiding resin combination deposits yields flake and gel, specifically, can add micro-hydrogen or micro-alcohols as molecular weight regulator, when adding micro-hydrogen, the ear that rubs during the gas phase that can control hydrogen and ethene is formed is lower than extremely; When adding the trace alcohol time-like, alcohol concentration is no more than 10ppm (weight) and is advisable in the solvent, and alcohols is ethanol or Virahol preferably, and this is characteristics of the present invention.
In manufacturing processed of the present invention, under the configured in series that does not change reactor, engineering a, engineering b and engineering c can select order and carry out with optional, only that is to say the engineering of implementing in the reactor is replaced mutually, arrive engineering d at last again, be preferably from the order of engineering a → b → c → d, engineering a → c → b → d, engineering b → a → c → d, engineering b → c → a → d and engineering c → b → a → d and carry out the successive manufacturing.Such manufacturing order is very flexible, not only can do according to the characteristic of product and client's demand and adjust arbitrarily and design, and because the residence time of polyreaction prolongs, make activity of such catalysts significantly improve, and production efficiency increases, and cost descends.
In order to make the ethylene copolymer of resin combination of the present invention continuously, need obtain high molecular weight fraction present as the alpha-olefin of copolymerization monomer especially, therefore, must use catalyzer that good as far as possible copolymerization ability is provided, perhaps select advantageous conditions to be used for copolymerization, Z-type catalyst or metallocene catalyst should be used as the catalyzer that is used for this purpose, solid Z-type catalyst or solid metallocene catalyst should be used especially.
The high reactivity Z-type catalyst that uses in manufacturing processed of the present invention can use as at the special public clear 50-32270 of Japanese Patent, special public clear 52-13232, special public clear 52-36790, special public clear 52-36915, special public clear 53-6019, special public clear 54-25517, special public clear 56-5403, special public clear 62-54326 and the clear 50-31835 of Te Kai, the spy opens clear 50-95384, the spy opens clear 53-40696, the spy opens clear 54-161091, the spy opens clear 54-41985, the spy opens clear 55-729, the spy opens clear 55-149307, the spy opens clear 57-12006, U.S. Pat 4071674, Chinese patent CN97121914, Chinese patent CN98110609, Chinese patent CN01114011, Chinese patent CN1042034, Chinese patent CN1199054, Chinese patent CN1490343, the catalyzer manufacture method of mentioning among Chinese patent CN1508161 and the TaiWan, China patent TW7111813.And when using metallocene catalyst, can use as open flat 10-255194 Japanese patent laid-open 8-208717, spy, the spy opens the catalyzer manufacture method of mentioning among flat 10-296535 and the Chinese patent CN99802116 and also can both be met.
Embodiment below by reference comes the poly continuously manufacturing that the present invention relates to is done further explanation, yet the present invention also not only is confined to following examples; Unless point out in addition, all operations all carries out under nitrogen.
The testing method of the related physical parameter of resin combination of the present invention comprises:
(1) limiting viscosity [η] (unit: dl/g): in 135 ℃ naphthalane solution, measure.
(2) density (unit: g/cm
3): the method according to ASTM D1505 is measured.
(3) ESCR (unit: hr): measure by the method according to ASTM D1693.
(4) the Emhorn shock strength (unit: kg-cm/cm notch): measure by the method according to ASTM D256.
(5) the hydrostatic intensity of tubing short-term (unit: MPa): measure by the method according to ASTM D1599.
(6) bottle blowing inwall and outward appearance: processing temperature C1/C2/C3/C4/AD/D=180/180/180/180/180/180 ℃ according to the System of Hollow Blow Shaping Machine platform imposes a condition, carries out the judgement of gel or fish eyes.
(7) polyvinyl piping materials is extruded processing:
A. forcing machine: German Battenfeld company makes
B. screw diameter: 45 millimeters
C. size of pipe and tubing: 63 millimeters of diameters, 5.8 millimeters of thickness
D. extruder temperature: 190/195/200/200 ℃
E. die head temperature: 200/200/200/200/210/210/210/215/215 ℃
Embodiment 1～3
Catalyzer is according to the special public clear 62-54326 number preparation of Japanese Patent.Dry back is thoroughly blown with nitrogen and is driven 800 liters of autoclaves that agitator is housed of replace with ethene, adds rub the in the least catalyzer 6.24 of ear triethyl aluminum and preceding method gained of 245 liters of normal hexanes, 247 in regular turn and restrains.Temperature in the kettle keeps 80 ℃, feeds ethene, 1-butylene and hydrogen continuously, and stagnation pressure remains on 0.9 MPa (gauge pressure), and the ear ratio that rubs during the gas phase of control hydrogen and ethene is formed is 1.50, carries out the polyreaction of engineering a under 4 hours the condition of polymerization time.Then, enter the polyreaction of engineering b, temperature keeps 75 ℃, and stagnation pressure remains on 0.61 MPa (gauge pressure), polymerization time 2.5 hours, and the ear ratio that rubs in the gas phase of control hydrogen and the ethene composition is 0.31.Enter the polyreaction of the engineering c in the 3rd step subsequently again, temperature keeps 75 ℃, and stagnation pressure remains on 0.52 MPa (gauge pressure), polymerization time 1.5 hours, and the rub ear ratio of the gas phase of control hydrogen and ethene in forming be 0.06, then blows and drive ethene, hydrogen and 1-butylene, and temperature is reduced to 55 ℃.At last, enter the polyreaction of engineering d, temperature in the kettle keeps 50 ℃, under stagnation pressure 0.2 MPa (gauge pressure), feed ethene, 1-butylene and micro-hydrogen continuously and work as molecular weight regulator with the liquid phase pan feeding, polymerization time 0.5 hour, the ear ratio that rubs during the gas phase of control hydrogen and ethene is formed is 0.015, in this step, can access extra high molecular amount component and effectively avoid producing the ultra-high molecular weight component by adding micro-hydrogen, its molecular weight size is between high molecular and ultra-high molecular weight.
Reaction ends, and release of pressure, displacement, cooling are wherein done regulation and control to the ratio of amount of polymers under each condition, and the resin combination of final resulting ethylene copolymerization carries out polymerization activity and molecule quantitative analysis, and its result is disclosed in table 1.And carry out granulation with twin screw extruder after the resin combination powder drying to the ethylene copolymerization that produces, carry out the bottle blowing processing experiment with System of Hollow Blow Shaping Machine, then resin combination is carried out the measurement of molecular weight, density, ESCR, Emhorn shock strength and the judgement of gel, the hollow bottle blowing sample that obtains like this, not only the inwall of shaped material and outward appearance without any gel or fish eyes, have excellent ESCR and shock strength simultaneously, therefore be particularly suitable for being used for making the large-scale chemistry bucket more than 200 liters, the results are shown in table 1.
Comparative example 1
In embodiment 1, only carry out the successive polymerization reaction of engineering a and engineering b, wherein, the polymerization temperature of engineering a is controlled at 80 ℃, the polymerization temperature of engineering b is controlled at 75 ℃, and rub ear than carrying out the preparation of high molecular weight fraction present in forming by the gas phase of hydrogen among the control engineering b respectively and ethene and butylene and ethene, obtained the molecular weight of final product and density basically with embodiment 1 in approaching, the ESCR of the resin combination that obtains like this and shock strength are compared obviously relatively poor with result among the embodiment 1～3, a little gel is not only arranged, and polymerization activity the results are shown in table 1 also far below the resin combination among the embodiment 1～3.
Comparative example 2
In embodiment 1, only with engineering a, engineering b and engineering d polymerization generation tree oil/fat composition, wherein engineering d changes into production ultra-high molecular weight component.Dry back is thoroughly blown with nitrogen and is driven 800 liters of autoclaves that agitator is housed of replace with ethene, adds rub the in the least catalyzer 6.24 of ear triethyl aluminum and preceding method gained of 245 liters of normal hexanes, 247 in regular turn and restrains.Temperature in the kettle keeps 80 ℃, feeds ethene, 1-butylene and hydrogen continuously, and stagnation pressure remains on 0.85 MPa (gauge pressure), and the ear ratio that rubs during the gas phase of control hydrogen and ethene is formed is 1.48, carries out the polyreaction of engineering a under 3.0 hours the condition of polymerization time.Then, enter the polyreaction of engineering b, temperature keeps 75 ℃, stagnation pressure remains on 0.4 MPa (gauge pressure), polymerization time 2.5 hours, and the ear ratio that rubs in the gas phase of control hydrogen and the ethene composition is 0.16, then blow and drive ethene, hydrogen and 1-butylene, temperature is reduced to 55 ℃.At last, enter the polyreaction of engineering d, temperature in the kettle keeps 50 ℃, feeds ethene and hydrogen down continuously in stagnation pressure 0.2 MPa (gauge pressure), and polymerization time is 0.5 hour, and the ear ratio that rubs during the gas phase of control hydrogen and ethene is formed is 0.005.Reaction ends, and release of pressure, displacement, cooling are carried out polymerization activity and molecule quantitative analysis to the resin combination of final resulting ethylene copolymerization.And carry out granulation with twin screw extruder after the resin combination powder drying to the ethylene copolymerization that produces, carry out the bottle blowing processing experiment with System of Hollow Blow Shaping Machine, then resin combination is carried out the measurement of molecular weight, density, ESCR, Emhorn shock strength and the judgement of gel, the hollow bottle blowing sample that obtains like this is uneven, produce many tiny gels, and the ESCR of this resin combination compares obviously relatively poorly with the result of embodiment 1～3, the results are shown in table 1.
Embodiment 4
In embodiment 2, engineering d polymeric temperature in the kettle keeps 50 ℃, stagnation pressure remains under the situation of 0.2 MPa (gauge pressure) and feeds ethene and micro-1-butylene continuously in the liquid phase mode, polymerization time is 0.5 hour, work as molecular weight regulator but add micro-Virahol, the concentration of Virahol is 8ppm (weight) in the solvent, in this step, can access extra high molecular amount component equally and effectively avoid producing the ultra-high molecular weight component, its molecular weight size is between high molecular and ultra-high molecular weight.
Reaction ends, and release of pressure, displacement, cooling are carried out polymerization activity and molecule quantitative analysis to the resin combination of final resulting ethylene copolymerization.And carry out granulation with twin screw extruder after the resin combination powder drying to the ethylene copolymerization that produces, and carrying out the bottle blowing processing experiment with System of Hollow Blow Shaping Machine then, the hollow bottle blowing sample that obtains is not so still observed gel, the results are shown in table 1.
Comparative example 3
Carry out polyreaction with the method among the embodiment 1, but do not add any hydrogen fully among the engineering d, the hollow bottle blowing sample that obtains so but is uneven, has many tiny gels to produce, and the results are shown in table 1.
Embodiment 5
Dry back is thoroughly blown with nitrogen and is driven 800 liters of autoclaves that agitator is housed of replacing with ethene, add rub catalyzer 7.41 gram of ear triethyl aluminum and preceding method gained of 260 liters of normal hexanes, 262 millis in regular turn, temperature in the kettle keeps 80 ℃, except that 1-butylene, feed ethene and hydrogen continuously, stagnation pressure remains on 0.87 MPa (gauge pressure), and the ear ratio that rubs during the gas phase of control hydrogen and ethene is formed is 3.50, carries out the polyreaction of engineering a under 3.7 hours the condition of polymerization time.Then, enter the polyreaction of engineering b, feed 1-butylene, ethene and hydrogen more continuously, temperature keeps 75 ℃, and stagnation pressure remains on 0.61 MPa (gauge pressure), polymerization time 2.2 hours, and the ear ratio that rubs in the gas phase of control hydrogen and the ethene composition is 0.16.Enter the polyreaction of the engineering c in the 3rd step subsequently again, temperature keeps 75 ℃, and stagnation pressure remains on 0.52 MPa (gauge pressure), polymerization time 1.7 hours, and the rub ear ratio of the gas phase of control hydrogen and ethene in forming be 0.058, then blows and drive ethene, hydrogen and 1-butylene, and temperature is reduced to 55 ℃.At last, enter the polyreaction of engineering d, temperature in the kettle keeps 50 ℃, feeds ethene, 1-butylene and micro-hydrogen down continuously in stagnation pressure 0.2 MPa (gauge pressure) and works as molecular weight regulator, polymerization time is 0.4 hour, and the ear ratio that rubs during the gas phase of control hydrogen and ethene is formed is 0.044.
Reaction ends, and release of pressure, displacement, cooling are carried out polymerization activity and molecule quantitative analysis to the resin combination of final resulting ethylene copolymerization, and its result is disclosed in table 2.And carry out granulation with twin screw extruder after the resin combination powder drying to the ethylene copolymerization that produces, carry out the bottle blowing processing experiment with System of Hollow Blow Shaping Machine, then resin combination is carried out the measurement of molecular weight, density, ESCR and the judgement of gel, the hollow bottle blowing sample that obtains like this, not only the inwall of shaped material and outward appearance without any gel or fish eyes, also have excellent ESCR and shock strength (the Emhorn shock strength is 35).For further confirming to be applied to the feasibility of polyvinyl piping materials, after this resin combination granulation, preparing diameter with forcing machine again is 63 millimeters, thickness is 5.8 millimeters polyvinyl piping materials, and do explosion with the water test and test, not only show uniqueness " fish mouth shape " ductile failure (ductile failure) characteristic (can be with reference to following document, the summary of the various PE100 grades on the market is provided: " PE100 Resins for Pipe Applications:Continuingthe Development into the 21st Century " Scheirs etc., TRIP vol.4, No.12, pp408-415,1996), but also have the excellent hydrostatic intensity of short-term concurrently, the results are shown in table 2.
Comparative example 4
In embodiment 5, only carry out the polyreaction of engineering a and engineering b, the polymerization temperature of engineering a is controlled at 80 ℃, polymerization time 3.0 hours, the polymerization temperature of engineering b is controlled at 75 ℃, polymerization time 2.0 hours, and carry out the preparation of high molecular weight fraction present, the molecular weight of the final product that obtains like this and density by regulating among the engineering b gas phase mol ratio of ethene and hydrogen and ethene and 1-butylene basically with embodiment 5 in approaching.Similarly, after this resin combination granulation, preparing diameter with forcing machine again is 63 millimeters, wall thickness is 5.8 millimeters a polyvinyl piping materials, and do explosion with the water test and test, tubing then presents " non-fish mouth shape " brittle rupture (brittle failure) characteristic, it is obviously poor that the hydrostatic intensity of short-term is compared with embodiment 5, the results are shown in table 2.
Embodiment 6
Carry out polyreaction with the method with embodiment 5, but use 1-butylene instead the 1-hexene, the rerum natura result who obtains is disclosed in table 2, still has the hydrostatic intensity of high ESCR and short-term.
Table 1
| Engineering a | Engineering b | Engineering c | Engineering d | The resin combination of ethylene copolymer | |||||||||||
| Alpha-olefin | Polymerization amount wt% | Alpha-olefin | Polymerization amount wt% | Alpha-olefin | Polymerization amount wt% | Alpha-olefin | [η] dl/g | Polymerization amount wt% | [η] dl/g | Density g/cm 3 | ESCR hr | Emhorn shock strength kg-cm/cm notch | Inwall and outward appearance | Active kgPE/gTi | |
| Execute example 1 | 1-butylene | 28.0 | 32.0 | 1-butylene | 36.0 | - | 9.02 | 4.0 | 2.72 | 0.950 | 600 | 40 | Well | 1505 | |
| Execute example 2 | 1-butylene | 32.5 | 28.5 | 1-butylene | 35.5 | 1-butylene | 8.78 | 3.5 | 3.50 | 0.953 | ＞1000 | NB | Well | 2033 | |
| Embodiment 3 | - | 32.5 | 1-butylene | 28.5 | - | 34.8 | 1-butylene | 9.21 | 4.2 | 3.81 | 0.953 | ＞1000 | NB | Well | 1995 |
| Comparative example 1 | 1-butylene | 50.0 | - | 50.0 | - | - | - | - | - | 2.65 | 0.951 | 121 | 21 | A little gel | 515 |
| Comparative example 2 | 1-butylene | 48.0 | - | 48.5 | - | - | - | 13.61 | 3.5 | 3.62 | 0.949 | 95 | 47 | Gel is many | 1005 |
| Embodiment 4 | 1-butylene | 32.5 | - | 28.5 | 1-butylene | 35.5 | 1-butylene | 8.45 | 3.5 | 3.47 | 0.949 | 850 | 50 | Well | 1497 |
| Comparative example 3 | 1-butylene | 28.0 | - | 32.0 | 1-butylene | 36.0 | - | 10.89 | 4.0 | 2.85 | 0.950 | 387 | 51 | Gel is many | 1489 |
(NB refers to No breaking, not fracture)
Table 2
| Engineering a | Engineering b | Engineering c | Engineering d | The resin combination of ethylene copolymer | |||||||||||
| Alpha-olefin | Polymerization amount wt% | Alpha-olefin | Polymerization amount wt% | Alpha-olefin | Polymerization amount wt% | Alpha-olefin | [η] dl/g | Polymerization amount wt% | [η] dl/g | Density g/cm 3 | ESCR hr | The hydrostatic intensity MPa of short-term | Inwall and outward appearance | Active kgPE/gTi | |
| Embodiment 5 | - | 41.5 | 1-butylene | 28.6 | - | 26.2 | 1-butylene | 8.98 | 3.7 | 2.83 | 0.948 | ＞1000 | 6.1 | Well | 1166 |
| Comparative example 4 | 1-butylene | 60.0 | - | 40.0 | - | - | - | - | - | 2.52 | 0.947 | 150 | 4.2 | Gel is many | 526 |
| Embodiment 6 | - | 42.3 | The 1-hexene | 29.1 | - | 26.4 | The 1-hexene | 8.79 | 2.2 | 2.84 | 0.949 | ＞1000 | 6.0 | Well | 1254 |
Claims (4)
1. poly method for continuous production, be in four reactors of configured in series, starting monomer to be carried out polyreaction and mixing, it is characterized in that: at least one reactor wherein, except that necessary starting monomer, also use and contain (a) titanium at least, a kind of in the solid catalyst metallocene compound of magnesium and halogenide component and the solid catalyst of aikyiaiurnirsoxan beta, and (b) molectron of organo-aluminium compound, well carries out the engineering that the multistage successive polymerization mixes simultaneously with the reactor that other is supplied with starting monomer, make limiting viscosity [η] scope from 1.1 to 8.0 with resin combination at last, density range is from 0.935g/cm
3To 0.965g/cm
3Polyethylene, the engineering a.b that is carried out in each reactor wherein, the control condition of c.d is:
Engineering a: under 70～100 ℃ of temperature, (dl/g) Alathon of scope from 0.1 to 4.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt% of manufacturing limit viscosity [η];
Engineering b: under 60～90 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 1.0 to 7.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering c: under 60～90 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 1.0 to 7.0 or the alpha-olefin content ethylene copolymer from 0 to 10wt%;
Engineering d: under 40～70 ℃ of temperature, the Alathon of manufacturing limit viscosity [η] scope from 2.0 to 11.5 or the alpha-olefin content ethylene copolymer from 0 to 4.5wt%;
Wherein:
(1) content of the Alathon of engineering a, engineering b and engineering c manufacturing or multipolymer respectively accounts for the polymkeric substance total amount from 20wt% to 50wt%;
(2) content of the Alathon of engineering d manufacturing or multipolymer accounts for the polymkeric substance total amount from 0.5wt% to 10wt%;
(3) according to (engineering b amount of polymers+engineering c amount of polymers): engineering a amount of polymers=6/7～5/1 adjusts;
(4) engineering d uses hydrogen or alcohols to work as molecular weight regulator.
2. poly method for continuous production as claimed in claim 1, it is characterized in that: described engineering a, engineering b, engineering c and engineering d can make tactic arbitrarily change under described each control condition, but the configuration of placed in-line each reactor does not change, to carry out polyreaction.
3. poly method for continuous production as claimed in claim 1 is characterized in that: described polyethylene is Alathon or ethylene copolymer.
4. poly method for continuous production as claimed in claim 3 is characterized in that: described ethylene copolymer is an alpha-olefin content from 0 to 10wt% ethylene copolymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880993A (en) * | 2012-12-19 | 2014-06-25 | 旭化成化学株式会社 | Ethylene polymer, tensile molded body, microporous membrane and diaphragm for battery |
| WO2022161400A1 (en) | 2021-02-01 | 2022-08-04 | 中国石油化工股份有限公司 | Method for continuously producing ultra-high molecular weight polyethylene by using slurry polymerization |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880993A (en) * | 2012-12-19 | 2014-06-25 | 旭化成化学株式会社 | Ethylene polymer, tensile molded body, microporous membrane and diaphragm for battery |
| CN103880993B (en) * | 2012-12-19 | 2016-04-13 | 旭化成化学株式会社 | Ethene polymers and be drawn into body, microporous membrane and battery separator |
| WO2022161400A1 (en) | 2021-02-01 | 2022-08-04 | 中国石油化工股份有限公司 | Method for continuously producing ultra-high molecular weight polyethylene by using slurry polymerization |
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